WO2008047745A1 - Polymère de polyacrylonitrile, procédé de production du polymère, procédé de production d'une fibre de précurseur pour fibre de carbone, fibre de carbone et procédé de production de la fibre de carbone - Google Patents

Polymère de polyacrylonitrile, procédé de production du polymère, procédé de production d'une fibre de précurseur pour fibre de carbone, fibre de carbone et procédé de production de la fibre de carbone Download PDF

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Publication number
WO2008047745A1
WO2008047745A1 PCT/JP2007/070051 JP2007070051W WO2008047745A1 WO 2008047745 A1 WO2008047745 A1 WO 2008047745A1 JP 2007070051 W JP2007070051 W JP 2007070051W WO 2008047745 A1 WO2008047745 A1 WO 2008047745A1
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Prior art keywords
component
polymer
weight
carbon fiber
molecular weight
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PCT/JP2007/070051
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English (en)
Japanese (ja)
Inventor
Fumihiko Tanaka
Makoto Endo
Yuuki Okishima
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Toray Industries, Inc.
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Application filed by Toray Industries, Inc. filed Critical Toray Industries, Inc.
Priority to EA200970384A priority Critical patent/EA019306B1/ru
Priority to EP07829785.0A priority patent/EP2080775B1/fr
Priority to BRPI0715985-4A priority patent/BRPI0715985A2/pt
Priority to CN2007800433294A priority patent/CN101553511B/zh
Priority to MX2009003991A priority patent/MX2009003991A/es
Priority to US12/445,116 priority patent/US8822029B2/en
Publication of WO2008047745A1 publication Critical patent/WO2008047745A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • the present invention relates to a high-quality carbon fiber precursor fiber, a polyacrylonitrile polymer suitable for production of carbon fiber, a production method thereof, and a carbon fiber precursor using a solution of the polyacrylonitrile polymer.
  • the present invention relates to a method for producing fibers and carbon fibers. Furthermore, the present invention relates to a carbon fiber excellent in compressive strength and tensile elastic modulus, and a production method thereof.
  • Carbon fiber has higher strength / specific strength and specific elastic modulus than other fibers, so as a reinforcing fiber for composite materials, in addition to conventional sports and aerospace applications, automobiles and civil engineering 'It is also widely deployed in general industrial applications such as construction, pressure vessels and windmill blades, and there is a strong demand for further improvements in productivity and production stabilization.
  • PAN polyacrylonitrile
  • S polyacrylonitrile
  • a carbon fiber precursor fiber by wet spinning, dry spinning or dry wet spinning, it is heated in an oxidizing atmosphere at a temperature of 200 to 400 ° C. to convert to a flame resistant fiber, at least 1 000 Manufactured industrially by heating and carbonizing in an inert atmosphere at a temperature of ° C.
  • the productivity improvement of the PAN-based carbon fiber is also performed from the viewpoint of spinning, flame resistance or carbonization of the carbon fiber precursor fiber, and misalignment!
  • the productivity is limited by the critical spinning draft ratio associated with the characteristics of the PAN-based polymer solution and the critical draw ratio associated with the solidification structure.
  • the spinning speed is increased to improve productivity, the drawability will decrease, and if the spinning becomes unstable or the spinning speed decreases immediately, the production will stabilize but the productivity will decrease. There is a problem that it is difficult to achieve both stability improvement and stabilization.
  • the spinning method has a great influence on the critical spinning draft rate, and the viewpoint of the spinning method will be described.
  • the dry spinning method is a method in which a spinning solution is discharged from a die hole into a high-temperature gas atmosphere to evaporate the solvent and concentrate and solidify.
  • the take-up speed is the evaporation rate of the solvent, so the take-up speed is high.
  • the wet spinning method is a method in which a spinning solution is discharged from a die hole to a coagulation bath, but coagulation proceeds immediately after the spinning solution is discharged from the die hole, and therefore, the take-up speed is increased.
  • yarn breakage occurs at the force cap surface that increases the actual spinning draft rate, and there is a limit to setting a high take-up speed.
  • M w weight average molecular weight
  • Mn number average molecular weight
  • Patent Document 1 JP 59-21709
  • Patent Document 2 Japanese Patent Application Laid-Open No. 64-77618
  • Non-patent document 1 Journal of the Japan Society of Rheology 215, 25 (1997)
  • Patent Document 3 Japanese Patent Laid-Open No. 61-97415
  • Patent Document 4 Japanese Patent Laid-Open No. 3-180514
  • Patent Document 5 Japanese Patent Laid-Open No. 3-185121
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2004-91961
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-197278
  • an object of the present invention is to provide a polyacrylonitrile-based polymer suitable for producing a carbon fiber precursor fiber capable of increasing the spinning speed and increasing the spinning draft rate, and a method for producing the same. is there.
  • Another object of the present invention is to provide a method for producing a high-quality carbon fiber precursor fiber with less fluffing without impairing productivity by using a solution of the polyacrylonitrile-based polymer.
  • Another object of the present invention is to provide a method capable of stably producing a high-quality carbon fiber using the above-described high-quality carbon fiber precursor fiber even in a firing step.
  • Another object of the present invention is to provide a carbon fiber excellent in compressive strength and tensile elastic modulus without impairing productivity and processability, and a method for producing the same.
  • the polyacrylonitrile-based polymer of the present invention has the following constitution. That is, the polyacrylonitrile-based polymer of the present invention is a polyacrylonitrile-based polymer that includes a polymer containing acrylonitrile as a main component and satisfies at least one requirement selected from the following [a] to [d].
  • Z average molecular weight (Mz) measured by gel permeation chromatography (GPC) method is 800,000-6 million, and polydispersity (Mz / Mw) (Mw represents weight average molecular weight) 3. 0 ⁇ ; 10 ⁇ 0.
  • Z + 1 average molecular weight (Mz + 1) measured by GPC method is 3 million to 10 million, and polydispersity ( ⁇ + 1 / Mw) is 6.0 to 25.0.
  • the PAN-based polymer means a polymer composition containing a polymer having a composition of acrylonitrile of 70 mol% or more and capable of containing another polymer of 20% by weight or less. To do.
  • the content of a component having a molecular weight of 3 million or more measured by GPC method is 1 to 10%.
  • the weight average molecular weight ratio of the component A to the component B is 4 to 45.
  • the polyacrylonitrile-based polymer of the present invention is suitable for producing a carbon fiber precursor fiber.
  • the polyacrylonitrile-based polymer production method of the present invention is prepared by adjusting the polymer concentration with respect to the solvent of the component A to 0.;! To 5% by weight, and then mixing the component B with it. Alternatively, the monomer constituting the component B is mixed with it and the monomer is polymerized. [0022] According to a preferred embodiment of the method for producing a polyacrylonitrile-based polymer of the present invention, the polymer concentration of the A component with respect to the solvent is 5 wt% or less until the start of mixing of the B component.
  • the monomer composing B component is mixed with it to polymerize the monomer.
  • a step of additionally introducing a polymerization initiator in the meantime and superposing the remaining unreacted monomer the ratio of the first metered introduction amount of the polymerization initiator to the other metered introduction amount (the first metering amount)
  • the amount introduced is from 0.0001 to 0.1.
  • the polyacrylonitrile-based polymer solution of the present invention contains the polyacrylonitrile-based polymer.
  • the polyacrylonitrile-based polymer solution of the present invention has an elongation viscosity described later of lOOOOPa's or more.
  • the storage elastic modulus when the frequency measured by dynamic viscoelasticity is 50 rad / s and the storage when the frequency is 0.05 rad / s.
  • This is a polyacrylonitrile polymer solution having a modulus ratio of 5 to 500.
  • the viscosity when the shear rate is 20 s- 1 and the viscosity when the shear rate is 1 are measured with a cone-plate viscometer. Is a polyacrylonitrile-based polymer solution having a ratio of 10 to 50.
  • the method for producing a carbon fiber precursor fiber of the present invention has the following configuration. That is, the method for producing a carbon fiber precursor fiber of the present invention is a method for producing a carbon fiber precursor fiber in which a solution of a polyacrylonitrile-based polymer suitable for producing the carbon fiber precursor fiber is spun by a wet and wet spinning method. It is.
  • the spinning draft is taken as 12 to 100 times, and the draw ratio after the take-up is taken.
  • the rate is 10 to 35 times, or when dry and wet spinning, the coagulated yarn is taken up at a speed of 50 to 500 m / min, and the draw ratio after taking it is 10 to 35 times.
  • the carbon fiber production method of the present invention has the following configuration. That is, the carbon fiber production method of the present invention is obtained by subjecting the carbon fiber precursor fiber obtained by the above carbon fiber precursor fiber production method to flame resistance treatment in air at a temperature of 200 to 300 ° C. A carbon fiber that is pre-carbonized in an inert atmosphere at a temperature of 300 to 800 ° C, and then carbonized in an inert atmosphere at a temperature of 1, 000-3, 000 ° C! It is.
  • the carbon fiber is produced by carbonization tension of 5.9 to 13.0 mN / dTex-precursor fiber.
  • the carbon fiber of the present invention is measured by crystallite size (Lc (nm)), strand tensile modulus (YM (GPa)), electron spin resonance (sometimes abbreviated as ESR). This is a carbon fiber that satisfies the following formulas (1) to (3).
  • the present invention by using a PAN-based polymer solution that can increase the spinning speed and increase the spinning draft rate, high-quality carbon fiber with less fluffing without impairing productivity.
  • Precursor fibers can be produced. Since such a high-quality carbon fiber precursor fiber is used, the high-quality carbon fiber can be stably produced even in the firing process.
  • carbon fibers with excellent compressive strength, tensile modulus, tensile strength and quality are produced with good productivity and processability. be able to.
  • the inventors of the present invention have arrived at the present invention as a result of intensive studies in order to produce a high-quality carbon fiber precursor fiber without impairing productivity.
  • the polyacrylonitrile polymer of the present invention (sometimes abbreviated as PAN polymer) It contains a polymer mainly composed of talironitrile and satisfies at least one requirement selected from the following [ a ] to [d].
  • the requirement [a] in the PAN-based polymer of the present invention is a Z-average molecule measured by a gel permeation chromatograph (hereinafter abbreviated as GPC) method (the details of the measurement method will be described later).
  • the amount (hereinafter abbreviated as Mz) is 800,000 to 6 million
  • the polydispersity (Mz / Mw) (Mw represents the weight average molecular weight, hereinafter abbreviated as Mw) is 3.0 to ; 10.0.
  • Mz is preferably 2 million to 6 million, more preferably 2.5 million to 5 million, and further preferably 2.5 million to 4 million.
  • the polydispersity (Mz / Mw) is preferably 5.0 to 8.0, and more preferably 5.5 to 7.0.
  • the average molecular weight measured by the GPC method includes a number average molecular weight (hereinafter abbreviated as Mn), a weight average molecular weight (Mw), a z average molecular weight (Mz), and a Z + 1 average molecular weight (M).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz z average molecular weight
  • M w is more sensitive to the contribution of high molecular weight than Mn.
  • Mz is more sensitive to the contribution of high molecular weight than Mw, and Z + 1 average molecular weight (hereinafter abbreviated as M) is the contribution of high molecular weight.
  • the molecular weight distribution index obtained using the average molecular weight measured by the GPC method includes molecular weight distribution (Mw / Mn) and polydispersity (Mz / Mw and M / Mw).
  • the molecular weight distribution (Mw / Mn) force is monodispersed when Si, and the molecular weight distribution becomes broader around the low molecular weight side as the molecular weight distribution (Mw / Mn) force becomes larger.
  • the polydispersity (Mz / Mw) becomes larger than 1
  • the molecular weight distribution becomes broader around the high molecular weight side.
  • the polydispersity (M / Mw) becomes larger than 1
  • the molecular weight measured by the GPC method indicates the molecular weight in terms of polystyrene.
  • the molecular weight distribution (Mw / Mn) and the polydispersity (Mz / Mw) are different, according to the study by the present inventors, the molecular weight distribution ( Even if Mw / Mn) is set to 7.0, the polydispersity (Mz / Mw) does not necessarily become 3.0 or more.
  • the polydispersity (Mz / Mw) is large. If the Mz is in the range of 800,000 to 6 million, the polydispersity (Mz / Mw) is not less than 3.0. Strain hardening occurs, and the discharge stability improvement degree of the spinning solution containing the PAN-based polymer is sufficient. In addition, if the polydispersity (Mz / Mw) is too large, the strain hardening is too strong and the effect of improving the discharge stability of the spinning solution containing the PAN polymer may be reduced. When the polydispersity (Mz / Mw) is 10.0 or less in the range of -6 million, the improvement in the discharge stability of the spinning solution containing the PAN polymer is sufficient.
  • the polydispersity (Mz / Mw) is in the range of 3.0 to 10.0, if the Mz is less than 800,000, the strength of the precursor fiber may be insufficient. If Mz is larger than 6 million, it may be difficult to discharge.
  • the elution time is diluted to the extent that it does not depend on the dilution concentration (that is, the viscosity change is small), and in order to obtain detection sensitivity as much as possible.
  • the solvent flow rate and column selection should be made to accommodate a large injection volume and a broad molecular weight distribution.
  • the exclusion molecular weight of the column should be at least 10 million and set so that the peak does not tail.
  • the dilution concentration is 0.1 wt / vol% and the injection volume is measured under two conditions of 20 L and 200 L. If the data are different, the data for the injection volume of 200 L should be taken. To do.
  • the requirement [b] in the PAN-based polymer of the present invention is the M force measured by the GPC method 3 ⁇ 4 million
  • M is preferably
  • / Mw is preferably 7.0 to 17.0, more preferably 10.0 to 15.0.
  • Polydispersity (M / Mw) is more strongly reflected in high molecular weight materials than polydispersity (Mz / Mw)
  • the degree of improvement in the discharge stability of the spinning solution containing the AN polymer is sufficient. Also, if the polydispersity (M / Mw) is excessively large, strain hardening is too strong and PAN-based polymerization
  • the polydispersity (M / Mw) is 25.0 or less.
  • the ejection stability of the spinning solution containing the N-based polymer is sufficiently improved.
  • the polydispersity (M lw) is in the range of 6.0-25.0, and when the M force is less than 3 ⁇ 4 million, the obtained precursor
  • the strength of body fibers may be insufficient, and if M is greater than 10 million,
  • the requirement [c] in the PAN-based polymer of the present invention is a gel permeation chromatography multi-angle light scattering photometer (hereinafter abbreviated as GPC-MALLS; details of the measurement method will be described later).
  • the measured Mzm is 400,000-1 million and the polydispersity (Mzm / Mwm) is 3.0-10.0. Mzm is preferably 600,000 to 800,000.
  • the polydispersity (Mzm / Mwm) of the polymer is preferably 5.0 to 8.0, more preferably 5.5 to 7.0.
  • the molecular weight and molecular weight distribution measured by GPC-MALLS are based on the absolute molecular weight, and reflect the true value from the molecular weight distribution measured by the GPC method. However, GPC measurements are often sufficient.
  • Mzm is in the range of 400,000 to 1,000,000
  • polydispersity (Mzm / Mwm) is 3.0 or more
  • sufficient strain hardening occurs and the degree of improvement in the discharge stability of the PAN polymer is sufficient.
  • strain hardening is so strong that the degree of improvement in the discharge stability of the spinning solution containing the PAN polymer may be insufficient.
  • the polydispersity (Mzm / Mwm) is 10.0 or less, the ejection stability of the spinning solution containing the PAN polymer is sufficient.
  • the polydispersity (Mzm / Mwm) is in the range of 3 ⁇ 0–10.0, if the Mzm is less than 400,000, the strength of the resulting precursor fiber may be insufficient. If it is large, it may be difficult to discharge the spinning solution containing the PAN-based polymer.
  • the requirement [d] in the PAN-based polymer of the present invention is that the Z average turning radius (hereinafter abbreviated as Rz) measured by GPC-MALLS is 25 to 45 nm, and the ratio of Rz to Rw (Rz / Rw) (Rw represents a weight average turning radius, hereinafter abbreviated as Rw) is 1.3 to 2.5.
  • Rz is preferably 29-37 nm.
  • GPC-MALLS can investigate the rotation radius by using a multi-angle light scattering photometer as a detector. Broadening the molecular weight distribution on the high molecular weight side means connecting molecules with a small rotation radius by molecules with a large rotation radius, and introducing long-chain branching that only affects the effects of linear molecules. It is also possible to use a copolymer having a different affinity with the solvent. Therefore, controlling Rz / Rw is one of the means for improving discharge stability. If Rz is in the range of 25 to 45 nm, sufficient strain hardening occurs when Rz / Rw is 1.3 or more, and the degree of improvement in the discharge stability of the PAN polymer is sufficient.
  • Rz / Rw when Rz / Rw is excessively large, there is a molecule that has an excessively large radius of rotation, which may reduce the drawability in yarn making. If Rz is in the range of 25 to 45 nm, Rz / Rw If it is 2.5 or less, the ejection stability of the spinning solution containing the PAN polymer is sufficiently improved. Also, Rz is in the range of 25-45nm If Rz is less than 25 nm, the strength of the resulting precursor fiber may be insufficient, and if Rz is greater than 45 nm, it may be difficult to discharge the spinning solution containing the PAN-based polymer.
  • the molecular weight distribution (Mw / Mn) or (Mwm / Mnm) is as small as possible! / Smaller is preferred because the content of low-molecular components that tend to cause structural defects in the fiber is reduced.
  • the molecular weight distribution (Mw / Mn) or (Mwm / rather than polydispersity (Mz / Mw) or (Mzm / Mwm) is preferred.
  • Mnm) is preferably small. In other words, even if both the high molecular weight side and the low molecular weight side are broad, the discharge stability of the spinning solution containing the PAN polymer is small!
  • the low molecular weight side is as sharp as possible (low molecular weight The component content is low), and the polydispersity (Mz / Mw) or (Mzm / Mwm) is more than 1.5 times the molecular weight distribution (Mw / Mn) or (Mwm / Mnm) More preferably, it is 1. 8 times or more.
  • radical polymerization such as aqueous suspension and solution method, which is usually performed in the polymerization of acrylonitrile (AN)
  • the molecular weight distribution is broad on the low molecular weight side.
  • the molecular weight distribution (Mw / Mn) or (Mwm / Mnm) is greater than the polydispersity (Mz / Mw) or (Mzm / Mwm). Therefore, in order to obtain a polymer having a molecular weight distribution (Mw / Mn) or (Mwm / Mnm) smaller than the polydispersity (Mz / Mw) or (Mzm / Mwm), the PAN-based polymerization of the present invention described later is used.
  • the molecular weight distribution it is preferable to contain 1 to 10% of a component having a molecular weight of 3 million or more, and Mw is preferably 100,000 to 600,000. Component forces with a molecular weight of 3 million or more If the force is less than Sl%, strain hardening is weak, and the degree of improvement in the stability of spinning solution containing a PAN polymer from the die may be insufficient. Over% In some cases, strain hardening is too strong, and the degree of improvement in the discharge stability of the PAN polymer may be insufficient. From this viewpoint, it is more preferable to include 1 to 7% of a component having a molecular weight of 3 million or more, and it is more preferable to include 1 to 4%.
  • the content of components with a molecular weight of 3 million or more here is the value obtained from the molecular weight distribution curve drawn by the logarithm of the polystyrene equivalent molecular weight measured by the GPC method and the refractive index difference, and is the integrated value of the entire molecular weight distribution.
  • the ratio of the integrated area of the peak area with polystyrene equivalent molecular weight of 3 million or more is shown. Since the difference in refractive index substantially corresponds to the weight of molecules eluted per unit time, the integrated value of the peak area substantially corresponds to the weight mixing ratio.
  • the polyacrylonitrile polymer satisfying the requirements [a] and / or [b] in the PAN polymer of the present invention is composed of two types of polyacrylonitrile polymers (A component and B component) having different molecular weights (Mw). Can be obtained by a method of mixing. In the present invention, mixing means to finally obtain a mixture of component A and component B, and a specific mixing method is to mix force S, which will be described later, and each single component. It is not limited.
  • the Mw of the component A is preferably 1 million to 15 million, more preferably 100 million to 500 It is preferable that the Mw of the B component is 150,000 to 1 million. The greater the difference in Mw between component A and component B!
  • Mw of component A is greater than 15 million
  • productivity of the A component may decrease, and when the Mw of the B component is less than 150,000, the strength of the precursor fiber may be insufficient, so the polydispersity (Mz / Mw) is 10
  • Mw / Mw is 10
  • the weight average molecular weight ratio of the component A and the component B is 2 to 45. Is more preferably 4 to 45, still more preferably 20 to 45.
  • the weight ratio of component A / component B is preferably 0.001-0.3, preferably S, more preferably 0.005-0.2, still more preferably 0.01-0. 1. If the weight ratio of component A and component B is less than 0.001, strain hardening may be insufficient, and if it is greater than 0.3, In some cases, the discharge viscosity of the coalesced solution is too high, making it difficult to discharge.
  • the weight average molecular weight ratio of the component A and the component B is 1.2 to 30.
  • a certain force S is preferable, more preferably 4 to 30, and still more preferably 6 to 15;
  • the weight ratio of the A component / B component is 0.001-0.3, which is preferably S, more preferably 0.005-0.2, and still more preferably 0.01-0. 1. If the weight ratio of the A component and the B component is less than 0.001, strain hardening may be insufficient, and if it is greater than 0.3, the discharge viscosity of the polymer solution may increase so that the discharge becomes difficult.
  • the Mw and weight ratio is measured by dividing the peak of the molecular weight distribution measured by GPC at the shoulder or peak, and calculating the Mw and peak area ratio of each peak.
  • the polyacrylonitrile polymer satisfying the requirements [c] and / or [d] in the PAN polymer of the present invention is composed of two types of polyacrylonitrile polymers (Am component, Bm component) having different molecular weights (Mwm). Can be obtained by the method of mixing S).
  • the polyacrylonitrile polymer having a large Mwm measured by GPC-MA LLS is the Am component
  • the polyacrylonitrile polymer having a small Mwm is the Bm component.
  • the Mwm of the Am component is preferably 400,000 to 4,000,000, more preferably 700,000 to 200,000.
  • the Mw of the Bm component is preferably 50,000 to 300,000.
  • the difference between the Mwm of the Am component and the Bm component is large because it tends to increase the polydispersity (Mzm / Mwm) of the mixed polymer.
  • the Mwm force of the Am component is greater than 00000,000 May reduce the productivity of the Am component, and when the Mwm of the Bm component is less than 50,000, the strength of the precursor fiber may be insufficient, so the polydispersity (Mzm / Mwm) is 10 or less. It is preferable to do this.
  • the weight average molecular weight ratio of the Am component to the Bm component is preferably 2 to 30, more preferably 4 to 30, and still more preferably 6 to 30.
  • the weight ratio of the Am component / Bm component should be 0.001 ⁇ 0.3. It is preferably 0.005—0.2, and more preferably 0.01—0.1. If the weight ratio of the Am component to the Bm component is less than 0.001, strain hardening may be insufficient, and if it is greater than 0.3, the discharge viscosity of the polymer solution may increase so that the discharge becomes difficult. is there.
  • the Mwm and weight ratio are measured by dividing the peak of the molecular weight distribution measured by GPC-MALLS into shoulders and peak parts, and calculating the Mw and peak area ratio of each peak.
  • the polyacrylonitrile polymer satisfying the requirement [d] in the PAN polymer of the present invention can be obtained by a method of mixing two polyacrylonitrile polymers having different weight average rotation radii (Rw). I'll do it.
  • Rw of the Am component is preferably 36 to 200 nm, more preferably 50 to;! OOnm
  • Rw of the Bm component is preferably 15 to 35 nm.
  • Rm of the Bm component is less than 15 nm, the strength of the precursor fiber may be insufficient, so Rz / Rw is preferably 2.5 or less.
  • the ratio of the weight average rotation radius of the Am component to the Bm component is preferably 1.2 to 10 and more preferably 1.5 to 5.
  • the weight ratio of Am component / Bm component is preferably 0.001 ⁇ 0.25, more preferably 0.005 ⁇ 0.2, and still more preferably 0.01. —0. If the weight ratio of the Am component to the Bm component is less than 0.001, strain hardening may be insufficient, and if it is greater than 0.3, the discharge viscosity of the polymer solution may increase so that the discharge becomes difficult. .
  • the rotation radius of the polymer depends largely on the molecular weight and the branched structure, and it is easiest to control the molecular weight to control the Rw of the Am component and the Bm component. In the case of satisfying the requirement of [c], the same molecular weight configuration as that described in the means for achieving the requirement of [c] is preferable.
  • the rotation radius can be adjusted by adjusting the molecular weight.
  • Rw and weight ratio can be obtained by measuring A component and B component by GPC-MALLS, respectively.
  • a method of first dissolving the component A which is a high molecular weight product, is preferred.
  • the dissolved state of the high molecular weight component A is extremely important, and if there is a small amount of undissolved material, it becomes a foreign substance. Voids may form inside the carbon fiber
  • the method for producing the polyacrylonitrile-based polymer of the present invention is such that the polymer concentration of the component A with respect to the solvent is preferably 0.;! To 5% by weight, and then the component B is mixed. Or it is preferable to mix and polymerize the monomer which comprises B component.
  • the polymer concentration of the above component A is more preferably 0.3 to 3% by weight, and still more preferably 0.5 to 2% by weight. More specifically, the polymer concentration of the component A is more preferably a semi-dilute solution in which the polymers are slightly overlapped as a state of aggregation of the polymer.
  • the mixed state tends to be uniform, so that a dilute solution that becomes an isolated chain state is a more preferable embodiment.
  • the concentration of the dilute solution is determined by the intramolecular exclusion volume, which is determined by the molecular weight of the polymer and the solubility of the polymer in the solvent. This often maximizes the performance of the carbon fiber.
  • the above polymer concentration exceeds 5% by weight, there may be an undissolved product of component A, and when it is less than 0.1% by weight, it is a dilute solution depending on the molecular weight. Saturation, power, S many! / ,.
  • the method in which the concentration of the polymer with respect to the solvent of the component A is preferably 0.;! To 5% by weight, and then the component B is mixed and dissolved therein is also effective.
  • a method of mixing a monomer obtained by diluting a high molecular weight material with a solvent and a monomer constituting the component B and mixing the solution by solution polymerization is preferred.
  • the method of adjusting the concentration of the polymer to the solvent of the component A to 0.;! To 5% by weight may be a method in which the polymer is dissolved in a solvent and then diluted, or a method in which polymerization is performed from a monomer.
  • the preferred dilution time is 50 to 120 ° C.
  • the dilution time varies depending on the dilution temperature and concentration before dilution. What is necessary is just to set suitably. If the dilution temperature is less than 50 ° C, dilution may take time S, and if it exceeds 120 ° C, component A may be altered.
  • the mixing of the B component starts from the production of the A component, or the monomer constituting the B component.
  • the polymerization is stopped when the polymer concentration is 5% by weight or less, and the component B is mixed therewith, or the monomer constituting the component B is mixed. This is a method of polymerizing the monomer.
  • component A is produced by introducing a polymerization initiator into a solution containing a monomer containing acrylonitrile (sometimes abbreviated as AN) as a main component and solution polymerization is completed.
  • AN acrylonitrile
  • a separate polymerization initiator is additionally introduced during the process until the B component is produced by solution polymerization of the remaining unreacted monomer, and the ability to obtain an AN polymer composition in which the A component and the B component are mixed S can. That is, according to a preferred embodiment of the method for producing the PAN-based polymer composition of the present invention, the polymerization initiator is metered in at least twice, and the first metered amount of the polymerization initiator and the others.
  • the ratio of the amount of metered introduction (the first metered amount introduced / the amount of other metered introductions) should be 0.1 or less, preferably 0.01 or less, more preferably 0.003 or less 1 Since the molecular weight tends to increase as the amount of the polymerization initiator is smaller, it is necessary if the ratio of the metered amount (the first metered amount / the other metered amount) exceeds 0.1. Mw may be difficult to obtain. On the other hand, the amount of polymerization initiator is small In this case, the polymerization rate becomes slow and the productivity tends to decrease. Therefore, the lower limit of the ratio of the metered introduction amount (the first metered amount introduced / the other metered amount introduced) is preferably 0.0001.
  • the most important thing is the amount of radicals generated by the polymerization initiator.
  • the preferred range can be changed by adjusting the polymerization temperature for the first and subsequent polymerizations and the type of polymerization initiator.
  • the preferable range of the ratio of the force to be applied and the amount of metered introduction is within the range of 0.0001 to 0.1.
  • each metering amount in the first round is the molar ratio of AN to the polymerization initiator.
  • (polymerization initiator / aN) is preferably from 1 X 10_ 7 1 X 10_ 4 , metered amount of second and subsequent is introduced into until then being, Ru aN all (Do any reaction unreacted ! /,) and the molar ratio of the polymerization initiator (polymerization initiator / aN) is preferably from 5 X 10- 3 from 5 X 10- 4.
  • polymerization initiator oil-soluble azo compounds, water-soluble azo compounds and peroxides are preferred from the viewpoint of safety handling and industrially efficient polymerization.
  • a polymerization initiator having a radiocanore generation temperature in the range of 30 to 150 ° C, more preferably in the range of 40 to 100 ° C is preferably used.
  • an azo compound that does not cause oxygen generation that inhibits polymerization at the time of decomposition is preferably used, and in the case of polymerization by solution polymerization, an oil-soluble azo compound is preferably used from the viewpoint of solubility.
  • polymerization initiators include 2, 2 'azobis (4-methoxy 2,4 dimethylvaleronitrile) (radical generation temperature 30 ° C), 2, 2' azobis (2, 4'-dimethylvaleronitrile). (Radical generation temperature 51 ° C) and 2,2'-azobisisoptyronitrile (radical generation temperature 65 ° C). Even if the same polymerization initiator is used for the first and other polymerization initiators, the force, wrap-around V, and the radical amount generated by the polymerization initiator can be adjusted by combining multiple polymerization initiators and the polymerization temperature. You can also Also, when using peroxides, it is possible to promote the generation of radicals by coexisting reducing agents!
  • the preferred range of the polymerization temperature varies depending on the type and amount of the polymerization initiator, but it is preferable. Or 30 ° C or more and 90 ° C or less.
  • the polymerization temperature is less than 30 ° C, the amount of radicals generated by the polymerization initiator decreases, and when a polymerization initiator with a low radical generation temperature is used, storage is often difficult, and the polymerization temperature exceeds 90 ° C. It is often higher than the boiling point of AN, making production control difficult.
  • the polymerization after the introduction of the first polymerization initiator and the polymerization after the introduction of the second and subsequent polymerization initiators may be performed at the same polymerization temperature or at different polymerization temperatures.
  • the measurement of the weight content of the A component relative to the total polymer is as follows. When mixing with the B component, measure the weight of the A component before mixing and the weight of the PAN-based total polymer composition after mixing. It can be calculated from the weight percentage. In addition, when the monomer constituting the B component is mixed and solution polymerization of the monomer is performed, the polymerization initiator for polymerizing the B component is polymerized after the A component is polymerized. Measure the polymerization rate of component A, measure the weight of component A in the solution, and separately determine the weight of the PAN-based total polymer determined from the polymer composition concentration of the PAN-based total polymer composition solution. It can be measured and calculated from its weight percentage.
  • the component A preferably used in the present invention is preferably a PAN-based polymer from the viewpoint of compatibility, which is desirably compatible with PAN.
  • the composition is preferably atorilonitrile, preferably 98 to; 100 mol%, and may be copolymerized if the monomer copolymerizable with AN is 2 mol% or less, but the chain transfer constant of the copolymerization component is If it is difficult to obtain Mw that is smaller than AN, it is preferable to reduce the amount of copolymerization component!
  • Examples of the monomer copolymerizable with AN in the component A of the present invention include acrylic acid, methacrylic acid, itaconic acid and alkali metal salts thereof, ammonium salts and lower alkyl esters, acrylamide and derivatives thereof. , Aryl sulfonic acid, methallyl sulfonic acid and salts or alkyl esters thereof can be used.
  • flame resistance can be achieved with a small amount of copolymerization, which is preferable from the viewpoint of improving the tensile strength of carbon fibers, which can be obtained by making the B component and the degree of acceleration of flame resistance almost equal. Itaconic acid is particularly preferred for promoting the conversion.
  • the polymerization method for producing the PAN-based polymer as component A can be selected from a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like.
  • a solution polymerization method for the purpose of uniformly polymerizing AN and copolymer components, it is preferable to use a solution polymerization method.
  • a solvent in which PAN is soluble such as an aqueous solution of zinc chloride, dimethyl sulfoxide, dimethylformamide and dimethylacetamide, is preferably used.
  • a solvent having a large chain transfer constant that is, a solution polymerization method using a zinc chloride aqueous solution or a suspension polymerization method using water is also preferably used.
  • the composition of the PAN polymer which is the B component preferably used in the present invention, is AN, preferably 98 to 100 mol%, and 2 mol of a monomer copolymerizable with AN. If it is less than%, copolymerization may be possible! /, But as the amount of the copolymerization component increases, molecular breakage due to thermal decomposition at the copolymerization portion becomes more prominent, and the tensile strength of the resulting carbon fiber decreases.
  • the monomer copolymerizable with AN in the component B of the present invention includes, for example, acrylic acid, methacrylic acid, itaconic acid and alkali metal salts thereof, ammonium salts and lower alkyls from the viewpoint of promoting flame resistance.
  • Esters, acrylamide and derivatives thereof, allyl sulfonic acid, methallyl sulfonic acid and salts thereof or alkyl esters can be used.
  • the AN main chain is crosslinked with a copolymerizable monomer.
  • a monomer that can be copolymerized with AN in component B (meth) attalyloyl group-C linear or branched alkyl group X-linear or branched C
  • Alkyl group A compound represented by a (meth) atalyloyl group.
  • X may be substituted with cycloalkyl group, ester group, ester group C
  • a compound represented by a (meth) atalyloyl group is preferred.
  • Specific examples of the compound include ethylene glycol dimetatalylate, 1,3-butylene diol diatalylate, neopentyl glycol diatalylate, and 1,6-hexanediol diatalate.
  • the copolymerization amount of the copolymerizable monomer used for crosslinking cannot be generally stated because the appropriate value varies depending on the molecular weight of the polymer, but it is preferable to 100 mol parts of AN (or 0.001 to Monolayer, more preferably (0.01-0.3 to 0.3 monolayer, and more preferably 0.05-0.1 mol parts.
  • the polymerization method for producing the PAN-based polymer as component B can be selected from solution polymerization method, suspension polymerization method, emulsion polymerization method, etc.
  • a solution polymerization method for the purpose of uniformly polymerizing the components, it is preferable to use a solution polymerization method.
  • a solvent in which PAN is soluble such as an aqueous solution of zinc chloride, dimethyl sulfoxide, dimethylformamide and dimethylacetamide, is preferably used.
  • dimethyl sulfoxide is preferably used from the viewpoint of solubility of PAN.
  • the PAN polymer solution is a solution obtained by dissolving the PAN polymer in a solvent, and has an elongational viscosity of lOOOOPa's or more.
  • lOOOOPa's a solution obtained by dissolving the PAN polymer in a solvent
  • elongational viscosity preferably it is 5000 OPa's or more, more preferably lOOOOOPa's or more.
  • the upper limit of elongational viscosity is not particularly limited, but lOOOOOOPa's is often sufficient.
  • the extensional viscosity represents the difficulty of deformation at the time of extensional deformation.
  • the measurement itself is essential, it means the value measured as follows. That is, about 0.1 ml of a PAN polymer solution kept at a temperature of 35 ° C. was sealed so as not to protrude between a pair of 4 mm diameter circular plates (gap 2 mm) arranged coaxially and vertically.
  • the change in filament diameter is measured immediately after the plate is lifted, and the value calculated by the following equation is the average value of the three points from the side (Hereafter, the maximum value is! /, U).
  • D (t) represents the filament diameter at time t.
  • the above surface tension is measured using a platinum plate by the Wilhelmi method.
  • the measurement temperature is 35 ° C.
  • the above extensional viscosity can be measured using an extension viscometer CaBERl manufactured by Thermo Harke.
  • the elongational viscometer encloses a sample between a pair of coaxially and vertically arranged circular plates, pulls the upper plate up and holds it, and changes the filament diameter of the sample over time to the laser micrometer. To measure.
  • the filament diameter of the sample decreases with time, and finally The force S to break and the change in filament diameter tend to decrease rapidly, and the longer the force S to break, the higher the elongational viscosity.
  • the plate pulling speed When the plate pulling speed is slowed down to about 20 mm / min, the time to break may increase due to the strong influence of shear viscosity. Even if a polymer solution is used, the effect of increasing the spinning speed is not observed, and the plate pulling speed must be increased to 20 m / min or more.
  • the extensional viscosity is three times the shear viscosity, but if the shear viscosity is increased to increase the extensional viscosity, it becomes difficult to discharge from the die. For this reason, when the strain is small, it is preferable that strain hardening appears as the strain decreases and the strain viscosity increases and the stretch viscosity increases.
  • the ratio between the maximum value and the minimum value of the extensional viscosity is preferably 100 times or more, more preferably 1000 times or more. There is no upper limit for the ratio between the maximum and minimum values, but 100000 times is often sufficient.
  • the minimum value of the extensional viscosity is a value obtained by averaging three points from small values.
  • a PAN polymer solution can stabilize the flow and increase the spinning speed and increase the spinning draft rate.
  • Such a PAN polymer solution can be obtained by dissolving the PAN polymer in a solvent in which the PAN polymer is soluble such as dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.
  • the ratio of the storage elastic modulus when the frequency measured by dynamic viscoelasticity is 50 rad / s and the storage elastic modulus when the frequency is 0.05 rad / s is 5 in the PAN polymer solution of the present invention.
  • a force of ⁇ 500 S preferably 10 ⁇ ; 100, most preferably 20 ⁇ 50.
  • cohesive failure may occur when the polymer solution is discharged from the die, where the effect of the relaxation component contained in the polymer is strong, and the storage modulus ratio.
  • the force is greater than 00, capillary breakage may easily occur when the polymer solution is discharged from the die, in which the influence of the long-term relaxation component contained in the polymer is hardly observed.
  • the storage elastic modulus decreases as the frequency decreases, and the slope approaches 2.
  • a component having a high molecular weight that is, blending a component having a long relaxation time
  • the shear deformation of the polymer is relaxed even on the low frequency side, and the frequency dependence is reduced.
  • the relaxation time is long. V, presuming that the components are intermolecular and difficult to break!
  • the ratio of the storage elastic modulus when the frequency measured by dynamic viscoelasticity is 50 rad / s and the storage elastic modulus when the frequency is 0.05 rad / s is as follows. Is the value measured. That is, as measured by the DMA method (dynamic mechanical analysis method), 0.3 mL of a polymer solution was set on a cone plate having a diameter of 25 mm and an angle of 0.0rad as a gap of 0.056 mm, a measurement temperature of 35.0 ° C, and a strain. It is a value calculated by taking the value at 0.05 rad / s and the value at 50 rad / s from the data measured by scanning the frequency from 0.05 to 5 Orad / s under the condition of 200%.
  • DMA method dynamic mechanical analysis method
  • the ratio of the shear viscosity when the shear rate is 20 s 1 and the shear viscosity when the shear rate is 2000 s 1 as measured with a cone plate viscometer is 10 to 10.
  • a force of 50 is preferable, more preferably 20-40.
  • the shear viscosity ratio is less than 10, the viscosity may be too high when the polymer solution is discharged from the die, and when the shear viscosity ratio is greater than 50, the polymer solution may be discharged from the die. Sometimes uneven discharge is likely to occur. Normally, when the shear rate dependence of shear viscosity is measured, the shear viscosity decreases as the shear rate increases.
  • the PAN polymer solution of the present invention has a high shear rate, that is, the polymer approaches and soon becomes entangled. Even in a state of passing, it is estimated that the shear viscosity decrease is low by maintaining high molecular weight and entangled components! There is a difference in the back pressure of each nozzle hole due to the temperature distribution in the die and the flow of the polymer solution, and the shear speed may be different. If the shear viscosity is less dependent on the shear rate, uneven discharge due to the difference in pressure on the back will be reduced. it can.
  • the ratio of the shear viscosity when the shear rate is 20 s- 1 and the shear viscosity when the shear rate is 2000 s 1 measured with a cone-plate viscometer is measured as follows. Say the value to be. That is, 0.3 mL of the polymer solution was set in a viscometer with a gap of 0.056 mm on a cone plate with a diameter of 25 mm and an angle of 0.04 rad, and the shear rate was set to S SSOOs 1 at a measurement temperature of 35.0 ° C. It is a value calculated by taking the value at 20 s-1 and the value at 2000 s 1 from the data measured by scanning up to.
  • the above-mentioned PAN-based polymer is mixed with dimethyl sulfoxide, dimethylformamide and dimethyl case.
  • a PAN polymer such as toamide is dissolved in a soluble solvent to form a spinning solution.
  • the PAN polymer solution may contain a solvent (so-called coagulant) such as water, methanol, ethanol, etc. that solidifies the PAN polymer as long as the PAN polymer does not coagulate.
  • a component such as a polymerization inhibitor may be contained up to 5% by weight based on the PAN polymer.
  • the polymer concentration of the PAN-based polymer solution is preferably in the range of 15 to 30% by weight, more preferably 17 to 25% by weight, and most preferably 19 to 23% by weight. If the polymer concentration is less than 15% by weight, the amount of solvent used increases and the coagulation rate in the coagulation bath is lowered, which is not economical, and voids are formed inside, and a dense structure may not be obtained. On the other hand, if the polymer concentration exceeds 30% by weight, the viscosity increases and spinning may be difficult. The polymer concentration of the spinning solution can be adjusted according to the amount of solvent used.
  • the polymer concentration is the weight percent of the PAN polymer contained in the PAN copolymer solution. Specifically, after the PAN copolymer solution is weighed, the measured PAN copolymer is dissolved in a solvent that does not dissolve the PAN copolymer and is compatible with the solvent used for the PAN copolymer solution. After mixing the polymer solution to remove the PAN copolymer solution, weigh the PAN copolymer. The polymer concentration is calculated by dividing the weight of the PAN copolymer after desolvation by the weight of the PAN copolymer solution before desolvation.
  • the viscosity of the PAN polymer solution at a temperature of 45 ° C is preferably in the range of 150 to 2,000 boise, more preferably 200 to 1,500 boise, and even more preferably 300. ⁇ ; 1,000 boise. If the solution viscosity is less than 150 boise, the formability of the spun yarn decreases, and therefore the speed at which the yarn exits from the die, that is, the spinnability tends to decrease. If the solution viscosity exceeds 2,000 boise, gelation tends to occur and stable spinning tends to be difficult.
  • the viscosity of the spinning solution can be controlled by controlling the amount of polymerization initiator and chain transfer agent.
  • the viscosity of the PAN-based polymer solution at a temperature of 45 ° C is determined by the B-type viscometer. Can measure more. Specifically, a PAN polymer solution placed in a beaker is immersed in a hot water bath adjusted to a temperature of 45 ° C. to adjust the temperature, and as a B-type viscometer, for example, Tokyo Keiki Co., Ltd. Using a B8L viscometer manufactured by Rotor, using rotor No.
  • the viscosity of the PAN polymer solution is 0 to; the range of 1,000 boise is measured at a rotor speed of 6 rpm, and the spinning solution The viscosity of 1,000 to 10,000 boise is measured at a rotor speed of 0.6 rpm.
  • the solution Before spinning the PAN-based polymer solution, from the viewpoint of obtaining high-strength carbon fibers, the solution is passed through, for example, a filter having an opening of 1 ⁇ m or less, and the polymer raw material and each process are passed through. V, it is preferable to remove mixed impurities.
  • the above-mentioned PAN-based polymer solution can suppress the generation of fluff by any spinning method of wet spinning, dry spinning or dry-wet spinning. Therefore, it is preferable to produce a carbon fiber precursor fiber in order to increase the spinning speed and increase the spinning draft rate.
  • the dry-wet spinning method is a spinning method in which a spinning solution is once discharged into the air from a die and then introduced into a coagulation bath to coagulate.
  • the spinning draft rate of the PAN-based polymer solution is preferably 12 to 100 times, and the spinning draft rate is more preferably 13 to 50 times, and still more preferably 13 to 35. Within double range.
  • the spinning draft rate is the surface speed (winding speed of the coagulated yarn) of the roller (first roller) having a driving source with which the spun yarn (filament) first contacts after leaving the die.
  • the discharge linear velocity is a value obtained by dividing the volume of the polymer solution discharged per unit time by the nozzle hole area. Therefore, the discharge linear velocity is determined by the relationship between the solution discharge amount and the nozzle hole diameter.
  • the PAN polymer solution exits from the die hole and comes into contact with the coagulation solution and gradually coagulates into a filament.
  • the spinning draft rate indicates the magnification at which the spinning solution is stretched before solidifying. That is, the spinning draft rate is expressed by the following formula.
  • the discharge linear velocity is preferably 0.;! To 30 m / min. When the discharge linear velocity is less than 0.1 lm / min, the productivity decreases. On the other hand, if the discharge linear velocity exceeds 30 m / min, the liquid level of the coagulation bath becomes noticeable and the resulting fineness may be uneven.
  • the winding speed of the coagulated yarn determined by the discharge linear speed and the spinning draft rate is preferably 50 to 500 m / min.
  • productivity decreases, and when the winding speed exceeds 500 m / min, the liquid level of the coagulation bath becomes noticeable and the resulting fineness tends to be uneven.
  • the diameter of the spinneret hole is preferably from 0.05 mm to 0.3 mm, more preferably from 0 .;! To 0.15 mm.
  • the diameter of the nozzle hole is smaller than 0.05 mm, it is necessary to discharge the spinning solution from the nozzle at a high pressure, which reduces the durability of the spinning device and makes it difficult to spin from the nozzle.
  • the diameter of the die hole exceeds 0.3 mm, it may be difficult to obtain a fiber having a single fiber fineness of 1.5 dtex or less.
  • the coagulation bath preferably contains a solvent such as dimethyl sulfoxide, dimethylformamide and dimethylacetamide used as a solvent for the PAN polymer solution and a so-called coagulation promoting component.
  • a solvent such as dimethyl sulfoxide, dimethylformamide and dimethylacetamide used as a solvent for the PAN polymer solution
  • a so-called coagulation promoting component it is preferable to use water as the coagulation accelerating component which does not dissolve the PAN polymer and is compatible with the solvent used in the PAN polymer solution.
  • the condition of the coagulation bath is that the concentration of the organic solvent that is preferably controlled so that the cross section of the coagulated yarn (single fiber) is a perfect circle is 70% or less of the critical bath concentration Is preferred! The concentration of the organic solvent is high, and the subsequent solvent cleaning process is lengthened, resulting in decreased productivity.
  • the concentration of the dimethyl sulfoxide aqueous solution is preferably 5 to 55% by weight, more preferably 5 to 30% by weight.
  • the temperature of the coagulation bath is preferably 10 to 30 ° C, more preferably 15 to 5 ° C, which is preferably controlled so that the fiber side faces are smooth. are preferred.
  • a carbon fiber precursor fiber is obtained through a water washing step, an in-bath drawing step, an oil agent application step, and a drying step. .
  • the solidified yarn may be directly stretched in the bath without the water washing step, or may be stretched in the bath after the solvent is removed by the water washing step. Stretching in the bath is usually preferred to be performed in a single or multiple stretching baths that are temperature controlled to 30-98 ° C! /. At that time, the draw ratio is preferably! To 5 times, more preferably 1 to 3 times.
  • an oil agent composed of silicone or the like to the drawn fiber yarn for the purpose of preventing adhesion between single fibers. It is preferable to use a silicone oil containing a modified silicone such as amino-modified silicone having high heat resistance.
  • a known method can be used for the drying step. For example, drying conditions with a drying temperature of 70-200 ° C and a drying time of 10 to 200 seconds are preferred! / Give results.
  • a heating heat medium for example, pressurized steam or superheated steam is preferably used in terms of operation stability, and the draw ratio is preferably 1.5 to 10 times.
  • the total draw ratio from the winding of the coagulated yarn is preferably 10 to 35 times, by using the polymer of the present invention, a high spinning draft rate and a high combination after winding the coagulated yarn. The total draw ratio is achieved.
  • the single fiber fineness of the carbon fiber precursor fiber obtained in this way is preferably 0.01 to 1.5 dtex, more preferably 0.05 to 1. Odtex, and still more preferably. 0.1 to 0.8 dtex. If the single fiber fineness is too small, the process stability of the yarn making process and the carbon fiber firing process may be reduced due to the occurrence of thread breakage due to contact with rollers or guides. On the other hand, if the single fiber fineness is too large, the difference between the internal and external structures of each single fiber after flame resistance will increase, and the processability in the subsequent carbonization process will decrease, and the tensile strength and tensile modulus of the resulting carbon fiber will decrease. There is.
  • the single fiber fineness (dtex) in the present invention is the weight (g) per 10,000 m of single fiber.
  • the degree of crystal orientation of the carbon fiber precursor fiber of the present invention is preferably 85% or more, more preferably 90% or more. If the degree of crystal orientation is less than 85%, the strength of the resulting precursor fiber may be lowered.
  • the obtained carbon fiber precursor fiber is usually in the form of a continuous fiber (filament).
  • the number of filaments per one yarn (multifilament) is preferably 1,000,000-3,000,000, more preferably 12,000-3,000,000, and further preferably Is 24,000-2,500,000, most preferably 24,000-2,000,000.
  • the resulting carbon fiber precursor fiber has high drawability, so the single fiber fineness is small, so the number of filaments per yarn is preferably larger for the purpose of improving productivity, but too much In some cases, the flameproofing treatment cannot be uniformly applied to the inside of the bundle.
  • the carbon fiber precursor fiber produced by the above-described method was subjected to flameproofing treatment in the air at a temperature of 200 to 300 ° C, preferably while stretching at a stretch ratio of 0.8 to 2.5. Thereafter, in an inert atmosphere at a temperature of 300 to 800 ° C., pre-carbonization is preferably performed while stretching at a draw ratio of 0.9 to 1.5; and a maximum of 1,000 to 3,000 ° C.
  • pre-carbonization is preferably performed while stretching at a draw ratio of 0.9 to 1.5; and a maximum of 1,000 to 3,000 ° C.
  • carbon fibers are preferably produced by carbonization while drawing at a draw ratio of 0.9 to 1.1.
  • it is preferable to carbonize the carbonization tension from 5.9 to 13.
  • Om N / dTex-precursor fiber If the carbonization tension is less than 5.9 mN / dTex-precursor fiber, the relationship between the tensile modulus of elasticity and the crystallite size, which is the object of the present invention, may not be satisfied. Also, carbonization with carbonization tension exceeding that of 13. OmN / dTex-precursor fiber is not preferable because it may be difficult due to limitations on equipment such as a roll for conveying yarn.
  • the tension in the carbonization process refers to the tension (mN) measured before the roll on the exit side of the carbonization furnace, converted into per single fiber, and divided by the fineness (dTex) of the carbon fiber precursor fiber when it is completely dry. It shall be indicated by the value.
  • the preliminary carbonization treatment and the carbonization treatment are performed in an inert atmosphere, and examples of gases used in the inert atmosphere include nitrogen, argon, xenon, and the like. From such a viewpoint, nitrogen is preferably used.
  • pre-carbonization treatment Is preferably set to 500 ° C./min or less in the temperature range.
  • the maximum temperature in carbonization can be set to 1,200 to 3,000 ° C depending on the desired mechanical properties of carbon fiber. Generally, the higher the maximum temperature in carbonization, the higher the carbon fiber obtained.
  • the tensile modulus of the steel increases, the tensile strength reaches a maximum at around 1,500 ° C, so the maximum temperature for carbonization is 1,200-- for the purpose of increasing both tensile strength and tensile modulus.
  • 1, 700. Preferably it is C, more preferably 1, 300-1, 600. C
  • the maximum temperature of carbonization is 1, 700-2, 300 ° C. .
  • the maximum temperature of carbonization treatment increases the tensile modulus as the maximum temperature increases, but graphitization progresses and the carbon network surface buckles due to the growth and lamination of the carbon network surface.As a result, the compressive strength increases. Since temperature may decrease, the temperature in the carbonization process should be set taking into account the balance between the two.
  • the carbon fiber of the present invention thus obtained may be abbreviated as crystallite size (Lc (nm)), strand bow I tensile elastic modulus (YM (GPa)), and electron spin resonance (ESR). ) Is a carbon fiber in which the spin density (LS (spin / g)) of the localized electrons measured by (1) satisfies the following formulas (1) to (3).
  • Carbon fiber is a polycrystal composed of an infinite number of graphite crystallites.
  • Increasing the maximum temperature of carbonization increases the crystallinity of the crystallites, that is, rearrangement of the carbon network surface increases the crystallite size, and at the same time the crystal orientation advances, so the tensile modulus of carbon fiber increases.
  • tension is a condition that greatly affects the characteristics of carbon fibers during carbonization. When the tension is increased under other conditions during carbonization, the crystallite size Lc does not change, but the crystal orientation advances and only YM increases.
  • LS is a characteristic that decreases as the number of lattice defects decreases due to rearrangement of the carbon network surface. Even if molecular fracture occurs for some reason, it decreases as the rearrangement of the carbon network surface proceeds. In other words, LS reflects the fact that the smaller the value, the better the carbon network surface is developed, from the viewpoint of force corresponding to the generation of defects due to molecular breakage due to tension during carbonization. Until the crystallite size is less than 2.6 nm, the larger the crystallite size, the smaller this value.
  • the carbon fiber of the present invention is 50Lc + 250 ⁇ YM ⁇ 5 OLc + 320 in the range of 2.6 ⁇ Lc ⁇ 3.4, whereas the carbon fiber conventionally used is generally There is a relationship of 50Lc + 210 ⁇ YM ⁇ 50Lc + 240 in the range of 2.6 ⁇ L c ⁇ 3.4.
  • the carbon fiber of the present invention satisfies the LS force SO. 5 X 10 18 ⁇ LS ⁇ 2.2 X 10 18 .
  • the meaning that LS satisfies this range indicates that there are few lattice defects.
  • the compressive strength decreases.
  • the spin density of the localized electrons is 2.2 X 10 18 or higher.
  • the compressive strength decreases. Since it does not occur, the effect is saturated, and the tensile modulus should be improved by further stretching in the carbonization process.
  • the spin density of localized electrons indicates that the PAN-based polymer has a wide molecular weight distribution on the high molecular weight side when the carbon fiber precursor fiber used is manufactured, and the high molecular weight component bears stress during the stretching process. However, as the whole progresses in orientation, the precursor fiber has few fine defects, and can be controlled by the carbonization tension and carbonization temperature when producing the carbon fiber.
  • the crystallite size of the carbon fiber of the present invention is less than 2.6 nm, the crystallinity is low and the tensile elastic modulus is low. When it exceeds 3.4 nm, the compressive strength is low. As a structural member, the balance between tensile modulus and compressive strength is poor. In order to achieve a better balance, the crystallite size is preferably 2.6 to 3. Onm.
  • the crystallite size of the carbon fiber can be controlled by the carbonization temperature, and the crystallite size increases as the carbonization temperature increases.
  • the average single fiber diameter of the carbon fiber of the present invention is preferably 1.5 to 7.5 m, and more preferably 1 ⁇ 5 to 3 ⁇ 9 111. If the average single fiber diameter is less than 1.5 m, there may be a problem that productivity deteriorates. On the other hand, when the average single fiber diameter is larger than 7.5 m, the flame resistance treatment inside the single fiber becomes insufficient, and thus there may be a problem that the strand tensile elastic modulus is not improved. Therefore, it may be selected based on a balance between productivity and tensile elastic modulus. However, when the polymer solution of the present invention is used, the discharge stability is remarkably increased, so that the average single fiber diameter is 1.5 to 3.9. m is easy, and productivity is unlikely to decrease.
  • the obtained carbon fiber can be subjected to electrolytic treatment for surface modification.
  • Electrolytic solutions used for electrolytic treatment include acidic solutions such as sulfuric acid, nitric acid and hydrochloric acid, and sodium hydroxide.
  • Alkalis such as potassium hydroxide, tetraethylammonium hydroxide, ammonium carbonate and ammonium bicarbonate or salts thereof can be used as the aqueous solution.
  • the amount of electricity required for the electrolytic treatment can be appropriately selected according to the carbonization degree of the carbon fiber to be applied.
  • the electrolytic treatment can optimize the adhesion to the carbon fiber matrix in the resulting fiber-reinforced composite material, and the brittle fracture of the composite material due to excessive adhesion and the tensile strength in the fiber direction.
  • the problem of lowering and the problem of poor adhesion to resin with high tensile strength in the fiber direction and lack of strength properties in the non-fiber direction have been solved. Strength properties balanced in both directions of the fiber will be developed.
  • a sizing treatment can also be performed to impart a focusing property to the carbon fiber.
  • a sizing agent having good compatibility with the matrix resin or the like can be appropriately selected according to the type of resin used.
  • the carbon fiber obtained by the present invention can be produced by various molding methods such as autoclave molding as a pre-predder, resin transfer molding as a preform for textiles, etc. It is suitably used as a sports member such as an automobile member, a fishing rod and a golf shaft.
  • molding methods such as autoclave molding as a pre-predder, resin transfer molding as a preform for textiles, etc. It is suitably used as a sports member such as an automobile member, a fishing rod and a golf shaft.
  • Mw uses at least three types of monodispersed polystyrenes with different molecular weights and known molecular weights to create a calibration curve for elution time and molecular weight, and on that calibration curve, read the molecular weight in terms of polystyrene corresponding to the corresponding elution time. Asked.
  • CLASS-LC2010 manufactured by Shimadzu Corporation was used as the GPC device
  • those having molecular weights of 184000, 427000, 791000 and 1300000 were used, respectively.
  • Mw uses at least six types of monodispersed polystyrenes with different molecular weights and known molecular weights to create a calibration curve for elution time and molecular weight, and reads the molecular weight in terms of polystyrene corresponding to the corresponding elution time on the calibration curve. Asked.
  • CLASS-LC2010 manufactured by Shimadzu Corporation was used as the GPC device.
  • RID-10AV manufactured by Shimadzu Corporation was used as the refractive index detector, and monodispersed polystyrenes for preparing calibration curves having molecular weights of 184000, 427 000, 791000, 1300000, 1810000, and 4240000 were used, respectively.
  • the surface tension was measured by a Wilhelmi method using a platinum plate.
  • the measurement temperature was 35 ° C.
  • an extension viscometer CaBERl manufactured by Thermohaake was used.
  • Place 0.3 mL of the polymer solution in the apparatus use a cone plate with a diameter of 25 mm and an angle of 0.04 rad, a gap of 0.056 mm, a measurement temperature of 35.0 ° C, and a strain of 200%. It is a value measured by scanning up to ⁇ 50 rad / s.
  • ARES which is a DMA device manufactured by T.A. Instruments Inc., was used, the measurement was performed three times, and the average value was used.
  • a value measured by scanning to 1 was used, the measurement was performed three times, and an average value was used.
  • the inspection items were evaluated in three stages by counting the number of fluff and fluff while running a 6000 filament bundle at a speed of lm / min.
  • the evaluation criteria are as follows.
  • Grade 3 More than 16 fibers in 300m.
  • the inspection items were evaluated in three stages by counting the number of fluff and fluff while running a fiber bundle of 24000 filaments at a speed of lm / min after firing and before surface treatment / sizing treatment.
  • the evaluation criteria are as follows. 'Grade 1: Within 1 piece of 30m fiber
  • the resin-impregnated strands of carbon fiber to be measured are 3, 4 epoxycyclohexylmethyl-3, 4 epoxy cyclohexyl carboxylate (100 parts by weight) / 3 boron fluoride monoethylamine (3 parts by weight) / acetone (4 parts by weight) ) was impregnated into carbon fiber or graphitized fiber, and cured at a temperature of 130 ° C for 30 minutes.
  • the number of carbon fiber strands measured was 6, and the average value of each measurement result was taken as the tensile strength.
  • the spectrum of the obtained differential curve was integrated twice to calculate the signal intensity.
  • This signal intensity is measured using a standard sample with a known number of spins per weight (for example, a polyethylene film subjected to ion implantation in which the number of spins is quantified using copper sulfate pentahydrate as a standard sample). Converted to spin number.
  • y ax + b, where y is the number of spins per weight at each temperature and X is the reciprocal of the absolute temperature of the measured temperature, the least squares method is used.
  • the coefficients a and b were obtained, and the spin number of the coefficient a was defined as the spin density (spin / g) of the localized electron.
  • .X-ray source CuKa line (tube voltage 40 kV, tube current 30 mA)
  • the weight A (g / m) and specific gravity B (g / cm 3 ) per unit length are determined for a carbon fiber bundle composed of a large number of carbon filaments to be measured.
  • the number of filaments of the carbon fiber bundle to be measured was C, and the average single fiber diameter (m) of the carbon fiber was calculated by the following formula.
  • Phenolic nopolac polyglycidyl ether resin 27% by weight
  • the obtained resin composition is applied to the silicone surface of the release paper to which silicone is applied to prepare a resin film.
  • the prepared resin film has a circumference of about 2.7 m.
  • the resin composition was wound around the surface of a steel drum adjusted to a temperature of 60 to 70 ° C. with the surface of the resin composition facing outward.
  • the carbon fiber bundle unwound from the creel is arranged on the surface of the resin composition wound around the steel drum via a traverse. Further, the resin film is covered with the resin film side facing the carbon fiber bundle side, and the resin film is pressed on the surface of the outer resin film while a separately prepared roll is contact-rotated.
  • the fiber bundle was impregnated to prepare a unidirectional pre-preda with a width of 300 mm and a length of 2.7 m.
  • the fiber basis weight of the pre-preda was adjusted to 190-200 g / m 2 by changing the drum rotation speed and traverse feed speed.
  • Laminate multiple sheets of the resulting pre-preda with the fiber direction aligned in one direction treat at a temperature of 130 ° C and a pressure of 0.3 MPa for 2 hours to cure the resin, and laminate with a thickness of lmm
  • a sheet fiber reinforced composite material
  • thickness 1 ⁇ 0. lmm, width 12.7 ⁇ 0. 13mm, length 80 ⁇ 0. 013mm, gauge length 5 ⁇ 0 ⁇ A 13 mm specimen was cut out.
  • the reinforcing plate was fixed with an adhesive or the like, and the gauge part length was 5 ⁇ 0.13 mm.
  • “Vinyleg” (registered trademark) K, manufactured by Chisso Corporation, DICY7, manufactured by Japan Epoxy Resins Co., Ltd., and the above 3- (3, 4- As dichlorophenyl) 1, 1-dimethylurea, DCMU-99 (hardening agent) manufactured by Hodogaya Chemical Co., Ltd. was used.
  • the obtained PAN polymer powder was sufficiently washed with water and dried to obtain a dry polymer A.
  • the resulting dried polymer A had Mz, Mw and Mn of 5.8 million, 3.4 million and 1.4 million, respectively.
  • polymerization condition B After replacing the space in the reaction vessel with nitrogen, heat treatment under the following conditions (referred to as polymerization condition B) was carried out with stirring and polymerized by a solution polymerization method to obtain a PAN polymer solution.
  • Temperature increase from 30 ° C to 60 ° C (Temperature increase rate: 10 ° C / hour)
  • the prepared PAN-based polymer solution was prepared so that the polymer concentration was 20% by weight, and then ammonia gas was blown until the pH reached 8.5, while neutralizing itaconic acid. An ammonium group was introduced into the PAN polymer to prepare a spinning solution.
  • the elongational viscosity was measured using the obtained PAN polymer solution, it was 1.0 X 10 5 Pa 's, and the ratio of the maximum value to the minimum value was 1.7 X 10 4 .
  • the storage elastic modulus was measured by dynamic viscoelasticity using the obtained PAN polymer solution, the storage elastic modulus at a frequency of 50 rad / s was 486 Pa, and the frequency was 0.05 rad / s.
  • the storage elastic modulus at s was 1.3 Pa, and the ratio was 361.
  • the measured shear viscosity viscometer cone plate type the shear viscosity when shear rate of 20s 1, a 30 Pa 's, shear rate 2000s 1 Kino Noto shear viscosity is an 0.95 The ratio was 32.
  • the obtained PAN-based polymer solution was passed through a filter with an opening of 0.5 mm to 40 mm. At the temperature of C?
  • a coagulated yarn was obtained at a spinning draft ratio of 4, and washed with water, then stretched in 90 ° C warm water at a stretch ratio of 3 times in a bath, and further added with an amino-modified silicone-based silicone oil, 165 ° Drying was performed for 30 seconds using a roller heated to a temperature of C, pressurized steam stretching was performed, and the limit steam stretching ratio was measured. The product of the draw ratio 3 times in the bath and the limit steam stretch ratio was taken as the limit stretch ratio after solidification.
  • the carbon fiber precursor fiber was produced under the following conditions. Solidified yarn was obtained under the conditions of a discharge linear velocity of 7 m / min and a spinning draft rate of 24. The coagulated yarn thus obtained is After washing, the film was stretched at 90 ° C. in warm water at a stretch ratio of 3 times in a bath, and an amino-modified silicone silicone oil was added to obtain a stretched yarn in the bath. The drawn yarn in the bath thus obtained was dried for 30 seconds using a roller heated to a temperature of 165 ° C., seven yarns were combined, and the number of total filaments was 42000.
  • Pressurized steam stretching was performed under the steam stretching ratio condition to obtain a carbon fiber precursor fiber having a single fiber fineness of 0.1 ldtex and a filament number of 42000.
  • the quality of the obtained carbon fiber precursor fiber was excellent, and the yarn passing through the spinning process was stable.
  • the obtained carbon fiber precursor fiber was subjected to a flame resistance treatment for 90 minutes in the air having a temperature distribution of 240 to 260 ° C. while being stretched at a stretch ratio of 1.0 to obtain a flame resistant fiber.
  • the obtained flame-resistant fiber was pre-carbonized while being drawn at a draw ratio of 1.2 in a nitrogen atmosphere having a temperature distribution of 300 to 700 ° C., and further having a maximum temperature of 1500 ° C.
  • carbonization was performed with the draw ratio set to 0.97 to obtain continuous carbon fibers. At this time, the passing through the firing process was good and the deviation was good.
  • the obtained PAN-based polymer solution was prepared so that the polymer concentration was 25 wt%, and then ammonia gas was blown until the pH reached 8.5, while neutralizing itaconic acid. Ammonium group was introduced into the PAN polymer to prepare a spinning solution. Spinning / firing / evaluation was carried out in the same manner as in Example 1 except that the spinning solution was changed. The processability was good in both the yarn making process and the firing process, and the quality of the obtained carbon fiber precursor fiber and carbon fiber was good.
  • Example 3 8 parts by weight of the dried polymer A obtained in Example 1 was uniformly dissolved in 410 parts by weight of dimethyl sulfoxide, and further 100 parts by weight of AN, 1 part by weight of itaconic acid, and 2,2′-azobisisobutyrate as a radical initiator. 0.4 part by weight of nitrile and 0.1 part by weight of octyl mercabtan as a chain transfer agent were mixed and dissolved uniformly, and it was put in a reaction vessel equipped with a reflux tube and a stirring blade. After the space in the reaction vessel was purged with nitrogen, heat treatment was performed under polymerization condition B while stirring, and polymerization was performed by a solution polymerization method to obtain a PAN polymer solution.
  • the obtained PAN-based polymer solution was prepared so that the polymer concentration was 18 wt%, and then ammonia gas was blown until the pH reached 8.5, while neutralizing itaconic acid. Ammonium groups were introduced into the polymer to prepare a spinning solution. Spinning / firing / evaluation was carried out in the same manner as in Example 1 except that the spinning solution was changed. The processability was good in both the yarn-making process and the firing process, and the quality of the precursor fibers and carbon fibers obtained was good.
  • AN 100 parts by weight of AN, 0.011 part by weight of AIBN as a radical initiator, 2,2'-azobis 2,4 dimethinoreno relonitrinore 0.02 part by weight, and 1,1, -azobis (cyclohexane-1 carbonitryl) 0.02 part by weight
  • a portion was uniformly dissolved in 370 parts by weight of dimethyl sulfoxide, and it was put into a reaction vessel equipped with a reflux tube and a stirring blade. After replacing the space inside the reaction vessel with nitrogen, heat treatment was performed under the following conditions while stirring, and polymerization was performed by a solution polymerization method to obtain a PAN-based polymer solution A.
  • PAN-based polymer solution A and PAN-based polymer solution B were mixed so that the pure polymer weight ratio was 8:92, and the polymer concentration was adjusted to 20% by weight.
  • ammonium groups were introduced into the polymer while neutralizing itaconic acid to prepare a spinning solution.
  • Spinning / firing / evaluation was performed in the same manner as in Example 1 except that the spinning solution was changed. The processability was good in both the yarn-making process and the firing process, and the quality of the obtained precursor fiber and carbon fiber was good.
  • the carbon fiber bundles obtained under the following production conditions were evaluated.
  • Solidified yarn was obtained under the conditions of a discharge linear velocity of 7 m / min and a spinning draft rate of 3.
  • the coagulated yarn thus obtained is washed with water, then stretched in 90 ° C warm water at a stretch ratio of 3 times in a bath, and further added with an amino-modified silicone silicone oil to stretch the stretched yarn in a bath.
  • Got. The drawn yarn in the bath thus obtained was dried for 30 seconds using a roller heated to a temperature of 165 ° C., two yarns were combined, and the total number of filaments was 12000, and the water vapor drawing was 5 times.
  • the carbon fiber precursor fiber having a single fiber fineness of 0.8 dtex and a filament number of 12000 was obtained by stretching in a pressurized water vapor under a magnification condition.
  • the obtained carbon fiber precursor fiber was flameproofed for 90 minutes while being stretched at a stretch ratio of 1.0 in air having a temperature distribution of 240 to 260 ° C. to obtain flameproofed fibers.
  • the obtained flame-resistant fiber was pre-carbonized while being stretched at a draw ratio of 1.0 in a nitrogen atmosphere having a temperature distribution of 300 to 700 ° C., and further having a maximum temperature of 1500 ° C. In a nitrogen atmosphere, carbonization was performed with the draw ratio set to 0.97 to obtain continuous carbon fibers.
  • the strand properties of the obtained carbon fiber bundle were measured.
  • the strength was 5. OGPa and the elastic modulus was 300 GPa.
  • Example 2 5 parts by weight of the dry polymer A obtained in Example 1 was uniformly dissolved in 370 parts by weight of dimethyl sulfoxide, and further 100 parts by weight of AN, 1 part by weight of itaconic acid, and 2,2′-azobisisobutyrate as a radical initiator.
  • 0.4 part by weight of nitrile and 0.4 part by weight of octyl mercabtan as a chain transfer agent were mixed and dissolved uniformly, and the mixture was put into a reaction vessel equipped with a reflux tube and a stirring blade. After replacing the space in the reaction vessel with nitrogen, the above polymerization was conducted with stirring.
  • a heat treatment of condition B was performed, and polymerization was performed by a solution polymerization method to obtain a PAN polymer solution.
  • the obtained PAN-based polymer solution was prepared so that the polymer concentration was 22% by weight, and then ammonia gas was blown until the pH reached 8.5, while neutralizing itaconic acid. Ammonium group was introduced into the PAN polymer to prepare a spinning solution. Spinning / firing / evaluation was carried out in the same manner as in Example 1 except that the spinning solution was changed. The processability was good in both the yarn making process and the firing process, and the quality of the obtained carbon fiber precursor fiber and carbon fiber was good.
  • the PAN polymer solution B obtained in Example 4 was thoroughly washed with water and dried to obtain a dry polymer B.
  • 53 parts by weight of the PAN-based polymer solution A obtained in Example 4 was mixed with 325 parts by weight of dimethyl sulfoxide and dissolved for 6 hours at a temperature of 70 ° C. with stirring.
  • the polymer concentration with respect to the solvent was 2% by weight.
  • 92 parts by weight of the pulverized dry polymer B92 was mixed in the polymer solution and dissolved at a temperature of 70 ° C. for 12 hours with stirring.
  • the heat treatment was performed under the above-mentioned polymerization condition B while stirring, and polymerization was performed by a solution polymerization method to obtain a PAN polymer solution.
  • a solution polymerization method to obtain a PAN polymer solution.
  • inject ammonia gas until the pH reaches 8.5.
  • an ammonium group was introduced into the polymer while neutralizing itaconic acid to prepare a spinning solution.
  • the extensional viscosity was measured and found to be 8.7 X 10 4 Pa's, and the ratio of the maximum value to the minimum value was 1.6 X 10 4 .
  • Spinning / firing / evaluation was performed in the same manner as in Example 4 except that the spinning solution was changed. Both the yarn-making process and the firing process had good process passability, and the quality of the obtained precursor fibers and carbon fibers was good.
  • the strength was 6.2 GPa and the elastic modulus was 300 GPa.
  • AN 100 parts by weight of AN, 0.011 part by weight of AIBN as a radical initiator, and 200 parts by weight of dimethyl sulfoxide were mixed and placed in a reaction vessel equipped with a reflux tube and a stirring blade. After replacing the space in the reaction vessel with nitrogen, heat treatment was performed under the following conditions while stirring, and polymerization was performed by a solution polymerization method to obtain a PAN polymer solution.
  • the polymer concentration of the obtained PAN-based polymer solution with respect to the solvent was 1.5% by weight.
  • 170 parts by weight of dimethyl sulfoxide, 1 part by weight of itaconic acid, and AIBN0 as a radical initiator in the polymer solution 4 parts by weight and 0.1 part by weight of octyl mercabtan as a chain transfer agent were uniformly dissolved and placed in a reaction vessel equipped with a reflux tube and a stirring blade.
  • the heat treatment was performed under the above polymerization condition B while stirring, and polymerization was performed by a solution polymerization method to obtain a PAN polymer solution.
  • ammonia gas was blown until the pH reached 8.5 to introduce ammonium groups into the polymer while neutralizing itaconic acid, and the spinning solution was Produced.
  • Spinning / firing / evaluation was carried out in the same manner as in Example 1 except that the spinning solution was changed. The processability was good in both the yarn-making process and the firing process, and the quality of the obtained precursor fiber and carbon fiber was good.
  • the obtained PAN polymer powder was sufficiently washed with water and dried to obtain a dry polymer A. Mz, Mw and Mn of the obtained dry polymer A are 58 respectively.
  • the extensional viscosity was measured using the obtained PAN polymer solution, it was 7.3 X 10 2 Pa's, and the ratio of the maximum value to the minimum value was 1.0 X 10 2. It was. Moreover, when the storage elastic modulus was measured by dynamic viscoelasticity using the obtained PAN polymer solution, the storage elastic modulus at a frequency of 50 rad / s was 979 Pa, and the frequency was 0.05 ra. The storage elastic modulus at d / s was 0.44 Pa, and the ratio was 2240.
  • the shear viscosity at a shear rate of 20 s- 1 was 53 Pa's
  • the shear viscosity at a shear rate of 2000 s 1 was 0 ⁇ 55.
  • the ratio was 96.
  • the limiting spinning draft rate and the limiting water vapor stretching ratio were measured in the same manner as in Example 1. However, under the same conditions as in Example 1 where the critical spinning draft rate was low, the spinning process was not passed.
  • a carbon fiber precursor having a single fiber fineness of 0.7 dtex and a filament number of 6000 was obtained by setting the spinning draft rate to 4 and maintaining the total number of filaments of 6000 without spinning and performing pressurized water vapor stretching under conditions of 5 times the steam stretching ratio. I got fiber. The quality of the carbon fiber precursor fiber obtained is poor and the yarn passing through the spinning process is not stable. won. When the obtained carbon fiber precursor fiber was baked in the same manner as in Example 1 to obtain carbon fiber, many fluffs and yarn breakage occurred in the baking process.
  • the obtained PAN-based polymer is thoroughly washed with water, dried, dissolved in dimethyl sulfoxide so that the polymer concentration becomes 15% by weight, and then ammonia gas is blown until the pH reaches 8.5.
  • a spinning solution was prepared. Spinning / firing was performed in the same manner as in Comparative Example 1 except that the spinning solution was changed, but a lot of fluff was generated in both the spinning process and the firing process.
  • the obtained PAN-based polymer was thoroughly washed with water, dried, and dissolved in dimethyl sulfoxide so that the polymer concentration was 5% by weight to prepare a spinning solution. Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed. However, the critical spinning draft rate was low and the spinning process did not pass.
  • the resulting dried polymer D had Mz, Mw and Mn of 130,000, 70,000 and 30,000, respectively.
  • the obtained PAN polymer solution and the PAN polymer solution obtained in Comparative Example 2 were mixed at a weight ratio of 6: 4, and the polymer concentration was adjusted to 20% by weight.
  • ammonium groups were introduced into the polymer while neutralizing itaconic acid to prepare a spinning solution.
  • Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed. However, the critical spinning draft rate was low and the yarn making process was not passed.
  • the carbon fiber carbonized in Comparative Example 6 was further carbonized in a nitrogen atmosphere at a maximum temperature of 1850 ° C and the tension was set to 6.2 mN / dtex—precursor fiber. Carbon fiber was obtained.
  • the carbon fiber carbonized in Comparative Example 6 was further carbonized in a nitrogen atmosphere at a maximum temperature of 1950 ° C and the tension was set to 6.2 mN / dtex—precursor fiber. Carbon fiber was obtained. Furthermore, in a nitrogen atmosphere with a maximum temperature of 2050 ° C, the carbonization was performed for the third time with the draw ratio set to 1.01.
  • the carbon fiber carbonized in Comparative Example 6 was further carbonized in a nitrogen atmosphere at a maximum temperature of 1950 ° C and the tension was set to 6.2 mN / dtex—precursor fiber. Carbon fiber was obtained. Furthermore, in a nitrogen atmosphere with a maximum temperature of 2250 ° C, the carbonization was performed for the third time with the draw ratio set to 1.01.
  • Example 10 A PAN-based polymer solution was obtained by polymerization in the same manner as in Example 9 except that the holding time for the polymerization condition E was changed to 2 hours. Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • a PAN-based polymer solution was obtained by polymerization in the same manner as in Example 9 except that the holding time for the polymerization condition E was 3 hours. Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • Polymerization was carried out in the same manner as in Example 9 except that the retention time for the polymerization condition E was changed to 4 hours to obtain a PAN-based polymer solution.
  • Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • a PAN-based polymer solution was polymerized in the same manner as in Example 9 except that the space in the reaction vessel was purged with nitrogen to an oxygen concentration of OO ppm or less and the holding temperature of polymerization condition E was 65 ° C. Got. Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • a PAN-based polymer solution was obtained by polymerization in the same manner as in Example 13 except that the holding time for the polymerization condition E was 2 hours. Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • a PAN-based polymer solution was obtained by polymerization in the same manner as in Example 15 except that the amount of octyl mercabtan introduced in the first measurement was changed to 0.01 part by weight. Fi was spun in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • a PAN-based polymer solution was obtained by polymerizing in the same manner as in Example 15 except that 0.01 part by weight of octyl mercabtan introduced at the first time was introduced and the retention time of polymerization condition F was 6 hours. . Spinning was carried out in the same manner as in Comparative Example 1 except that the spinning solution was changed.
  • Continuous carbon fibers were obtained in the same manner as in Example 8, except that the carbonization treatment was performed with the draw ratio set to 1.01 and the tension set to 11.5 mN / dtex-precursor fiber.
  • the strength was 8.2 GPa
  • the elastic modulus was 370 GPa
  • the compressive strength was 1.9 GPa
  • the crystallite size was 2 nm
  • the spin density of localized electrons was 1.9 X 10 18 spins. / g.
  • the tension was set to 11.5 mN / dtex—precursor fiber, and the second carbonization treatment was performed. Carbon fiber was obtained.
  • the second carbonization treatment is set in a nitrogen atmosphere with a maximum temperature of 1950 ° C, and further in the nitrogen atmosphere with a maximum temperature of 2050 ° C, the stretch ratio is set to 1.01, and the third carbonization treatment is performed.
  • a carbon fiber was obtained in the same manner as in Example 18 except that.
  • Comparative Example 7 that is, spinning in the same manner as in Example 4) except that the spinning solution of Example 9 was used.
  • the carbonization is performed for the second time by setting the tension to 6.2 mN / dtex-precursor fiber in a nitrogen atmosphere at a maximum temperature of 1850 ° C.
  • Carbon fibers were obtained in the same manner as in Comparative Example 7 except that the spinning solution of Example 10 was used.
  • the strength was 7.0 GPa
  • the elastic modulus was 335 GPa
  • the compressive strength was
  • the crystallite size was 2 ⁇ lnm
  • the spin density of localized electrons was 2 ⁇ 6 X 10 18 spins / g.
  • the second carbonization treatment is set in a nitrogen atmosphere with a maximum temperature of 1950 ° C, and further in the nitrogen atmosphere with a maximum temperature of 2050 ° C, the stretch ratio is set to 1.01, and the third carbonization treatment is performed.
  • a carbon fiber was obtained in the same manner as in Example 21 except that.
  • the second carbonization treatment is set in a nitrogen atmosphere with a maximum temperature of 1950 ° C, and in a nitrogen atmosphere with a maximum temperature of 2250 ° C, the stretch ratio is set to 1.01, and the third carbonization treatment is performed.
  • a carbon fiber was obtained in the same manner as in Example 21 except that.
  • Example 11 carbon fibers were obtained in the same manner as in Example 20 except that the first and second carbonization tensions were set to 6.2 mN / dtex-precursor fibers.
  • Example 18 1850 11.5 1 Example 2.6 420 7.5 1.7 0.5 2.1 1 Example 19 1950 11.5 2050 1.01 3.1 470 7.2 1.6 0.5 2.1 1 Example 20 1850 6.2 One 2.6 385 6.5 1.6 1.3 5.4 1 Example 21 1850 6.2 One-2.6 385 6.6 1.7 0.8 5.4 1 Example 22 1950 6.2 2050 1.01 3.1 435 6.0 1.6 0.8 5.4 1 Example 23 1950 6.2 2250 1.01 3.4 470 5.6 1.6 0.7 5.4 1 Example 24 1850 6.2--2.6 385 6.4 1.6 1.3 5.4 1 Comparative example 6 1500 6.2 1 1 1 2.1 300 6.6 1.6 5.7 5.4 3 Comparative Example 7 1850 6.2 1-2.6 340 6.0 1.4 2.7 5.4 3 Comparative Example 8 1950 6.2 2050 1.01 3.1 385 5.3 1.4 2.6 5.4 3 Comparative Example 9 1950 6.2 2250 1.01 3.4 410 5.0 1.3 2.5 5.4 3 Industrial Applicability
  • a high-quality precursor fiber can be produced without impairing productivity by using a PAN-based polymer capable of performing high-speed spinning and a high spinning draft rate.
  • a PAN-based polymer capable of performing high-speed spinning and a high spinning draft rate.
  • body fibers high-quality carbon fibers can be stably produced even in the firing step, which is useful.

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Abstract

La présente invention concerne un polymère polyacrylonitrile comprenant un polymère principalement composé d'acrylonitrile et répondant à au moins une condition requise choisie parmi les conditions [a] à [d] : [a] la masse moléculaire moyenne de Z (Mz) telle que mesurée au moyen d'un procédé de chromatographie par perméation de gel est comprise entre 800 000 et 6 000 000, et le degré de polydispersion (Mz/Mw) est compris entre 3,0 et 10,0 (Mw représentant la masse moléculaire moyenne pondérale) ; [b] la masse moléculaire moyenne de Z + 1 (Mz+1) telle que mesurée au moyen d'un procédé CPG est comprise entre 3 000 000 et 10 000 000 et le degré de polydispersion (Mz+1/Mw) est compris entre 6,0 et 25,0 ; [c] la valeur Mzm telle que mesurée au moyen d'un procédé de chromatographie par perméation de gel/un procédé de spectrophotométrie par dispersion de la lumière à angles multiples est comprise entre 400 000 et 1 000 000 et le degré de polydispersion (Mzm/Mwm) est compris entre 3,0 et 10,0 ; et [d] le rayon de giration moyen de Z (Rz) tel que mesuré au moyen d'un procédé de chromatographie par perméation de gel/un procédé de spectrophotométrie par dispersion de la lumière à angles multiples est compris entre 25 et 45 nm et le rapport de la valeur Rz sur le rayon de giration moyen pondéral (Rz/Rw) est compris entre 1,3 et 2,5.
PCT/JP2007/070051 2006-10-18 2007-10-15 Polymère de polyacrylonitrile, procédé de production du polymère, procédé de production d'une fibre de précurseur pour fibre de carbone, fibre de carbone et procédé de production de la fibre de carbone WO2008047745A1 (fr)

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EA200970384A EA019306B1 (ru) 2006-10-18 2007-10-15 Полимер на основе полиакрилонитрила, способ его получения, раствор полимера на основе полиакрилонитрила, способ изготовления волокна-предшественника углеродного волокна и способ изготовления углеродного волокна
EP07829785.0A EP2080775B1 (fr) 2006-10-18 2007-10-15 Polymère de polyacrylonitrile, procédé de production du polymère, procédé de production d'une fibre de précurseur pour fibre de carbone, fibre de carbone et procédé de production de la fibre de carbone
BRPI0715985-4A BRPI0715985A2 (pt) 2006-10-18 2007-10-15 polÍmero com base em poliacrilonitrila, mÉtodo de produÇço de polÍmero com base em polacrilonitrila, soluÇço de polÍmero com base em poliacrilonitrila, mÉtodo de produÇço de uma fibra precursora de fibra de caborno, mÉtodo de produÇço de fibra de caborno e fibra de caborno
CN2007800433294A CN101553511B (zh) 2006-10-18 2007-10-15 聚丙烯腈类聚合物和其制造方法及碳纤维母体纤维的制造方法及碳纤维和其制造方法
MX2009003991A MX2009003991A (es) 2006-10-18 2007-10-15 Polimero en base a poliacrilonitrilo y metodo de produccion del mismo, metodo de produccion de fibra precursora de fibra de carbono, y fibra de carbono, y metodo de produccion de la misma.
US12/445,116 US8822029B2 (en) 2006-10-18 2007-10-15 Polyacrylonitrile polymer, method of producing the same, method of producing precursor fiber used for producing carbon fiber, carbon fiber and method of producing the same

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JP2006283652 2006-10-18
JP2006-283652 2006-10-18
JP2007056829 2007-03-07
JP2007-056829 2007-03-07

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BR (1) BRPI0715985A2 (fr)
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JPWO2018003836A1 (ja) * 2016-06-30 2018-06-28 東レ株式会社 炭素繊維束およびその製造方法
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WO2019244830A1 (fr) 2018-06-18 2019-12-26 東レ株式会社 Fibre de carbone et son procédé de production
KR20210019029A (ko) 2018-06-18 2021-02-19 도레이 카부시키가이샤 탄소 섬유 및 그의 제조 방법
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PT2080775E (pt) 2015-10-20
CN101553511A (zh) 2009-10-07
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CN102086538B (zh) 2013-03-27
EA020873B1 (ru) 2015-02-27
US8822029B2 (en) 2014-09-02
CN101553511B (zh) 2012-01-11
BRPI0715985A2 (pt) 2013-08-06
TWI422598B (zh) 2014-01-11
KR101342176B1 (ko) 2013-12-16
EA201100259A1 (ru) 2011-06-30
KR20090068370A (ko) 2009-06-26
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US20100003515A1 (en) 2010-01-07
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